Textile decorating



Patented Dec. 25, 1951' TEXTILE DECORATING Norman S. Cassel, Ridgewood,and Alfred '1. Oil!- lord, Fair Lawn, N. J., assignors to InterchemicalCorporation, New York, N. Y., a corporation of Ohio No Drawing. Originalapplication June 28, 1946,

Serial No. 680,056. Divided and this application June 14, 1950, SerialNo. 168,172

' 15 Claims.

This invention relates to the pigment-decoration of fabrics.Specifically, the present inven- Good color value can be obtained by theuse of an aqueous printing paste containing a water-insoluble pigmentand a hydrophilic colloid, the colloidal solution or dispersion 01'which in water presents a heterogeneous or discontinuous structure.

Typical of such hydrophilic colloids is starch, which is widely used forthis purpose despite the fact that the .resulting pigment printpossesses inferior crockiastness and washfastness.

Hydrophilic colloids, the aqueous colloidal solutions of which arehomogeneous, have also been used in the preparation of pigment printingpastes. Typical of such hydrophilic colloids are the Water-solublecellulose ethers, gum karaya, gum tragacanth, albumen, sodium alginate,and the like. Pigment prints made from such pastes, however, generallypossess relatively poor color value.

(The term heterogeneous as used herein means that the colloidal solutionor dispersion of a hydrophilic coloid in an aqueous medium possessesdiscontinuity of structure when it is viewed with an ordinary compoundmicroscope. The term homogeneous as used herein means that the colloidalsolution or dispersion of a hydrophilic colloid in an aqueous medium isclear and continuous and does not exhibit any structure when it isviewed with an ordinary compound microscope. It should be noted, howeverthat both types of colloidal solutions or dispersions show somestructure when they are viewed with an ultra-microscope.)

We have now discovered that a textile print having an unusually full andeven color value can be obtained with a dispersion of a pigment in ahomogeneous colloidal solution in an aqueous medium of a water-solublehydrophilic colloid, with elimination of the disadvantages ordinarilyencountered in the use of such a dispersion and without flocculation ofthe pigment during application of the dispersion to the fabric, bygelling a second hydrophilic colloid in the presence of thewater-soluble hydropliilic colloid under conditions under which thelatter remains in solution and printing a fabric with the resultingpigmented printing paste. Advantageously, in printing a textile inaccordance with our invention, we utilize as the printing paste such apigmented dispersion in whicha water-soluble thermosetting resin is alsodissolved so that theresulting printed fabric is rendered wash-fast. Ourinvention also includes the textile-printing composition and theresulting pigment-printed fabric.

In its simplest form our pigment printing composition comprisesessentially a dispersion of a water-insoluble pigment or dyestufi in ahomogeneous colloidal solution of a water-soluble hydrophilic colloid inan aqueous medium containing another hydrophilic colloid that has beengelled therein under conditions under which the watersoluble hydrophiliccolloid remains in solution. Advantagecusly, both hydrophilic colloidsare initially present as a common homogeneous colloidal solution in suchaqueous medium. Preferably, our printing composition comprises such adispersion of a pigment in which a water-soluble thermosetting resinisalso dissolved in the aqueous medium.

Any pigment can be incorporated into the present composition provided itis sufiiciently lightfast, does not bleed to any substantial extent indry-cleaning solvents such as naphtha and carbon tetrach oride, and issufliciently resistant to soap. Suitable pigments include thephthalocyanines, various metal oxides, carbon black,

water-insoluble vat and am dyestuffs, and the like. The particularpigment selected for a given printing operation will depend not only onits discersibility and on the required color, of course. but also on thenature of the finished goods.

Similarly, any water-soluble heat-setting resin may be employed in thepreparation of the present pigmented printing composition provided thatthe resulting heat-converted resin is sufllciently resistant to washingand is substantially insoluble in dry-cleaning solvents and providedthat no objectionable stiffness is imparted to the printed fabric by theheat-set resin. Moreover, since the heat-set resin appears to serve atleast in part as a binder to flx the pigment to the fabric, it must becapable of doing so even when only a small amount thereof isincorporated in the printing composition.

We have obtained especially good results with the use of water-solublethermosetting ureaaldehyde resins including water-soluble thermosettingurea-iormaldehyde resins and watersoluble thermosetting modifiedurea-formaldehyde resins, particularly water-soluble polyhydricalcohol-modified urea-formaldehyde resins, melamine-aldehyde resinsincluding water-soluble thermosetting melamine-formaldehyde resins andwater-soluble thermosetting modified melamine-formaldehyde resins,particularly watersoluble polyhydric alcohol-modifiedmelaminei'ormaldehyde resins, and mixed urea-melaminealdehyde resinsincluding water-soluble thermosetting, urea-melamine-formaldehyde resinsand water-soluble thermosetting modified urea-melamine-formaldehyderesins, particularly watersoluble polyhvdric alcohol-modifiedurea-melamine-formaldehyde resins. Other water-soluble hea-settingresins, meeting the above requirements, such as water-solublethermosetting phenol-formaldehyde resins and polyvinyl alcoholaldriyderesins may also be used, however. As with the pigment, the choice of theparticular water-soluble heat-setting resin employed will be governed toa large extent by the nature of the finished fabric. Moreover, in somecases the reactants from which the water-soluble resins are derived maythemselves be incorporated in the composition and the resin subsequentlyformed therefrom.

The two hydrophilic colloids forming the basis of the presentcomposition must be initially soluble in the aqueous medium thereof togive a common homogeneous colloidal solution, and at least one of themmust be water-soluble. Such a homogeneous solution of a hydrophiliccolloid can be converted to a heterogeneous dispersion by suitablemodification of the initial solution so that the hydrophilic colloid iscoagulated or gelled or thrown out of solution as a gelatinousprecipitate. Accordingly, it is a feature of our invention that the twohydrophilic colloids are so selected that one of them can be gelled bymodification of the initial common homogeneous colloidal solution, underconditions under which the other remains in solution, to introduce aheterogeneous structure 'or discontinuity into such solution. It is thisconvertibility characteristic of such a, hydrophilic colloid that isutilized in obtaining the unusual results of our invention.

The discontinuity or heterogeneous structure imparted to the commonhomogeneous solution by gelation of one of the two hydrophilic colloidstherein appears to be the reason for the improved and unusual colorvalue obtained with such a pigmented printing composition. The resultingprint not only possesses a full and even color but does not evidence anyflocculation of the pigment. In contrast, a print made from a pigmentedhomogeneous solution of either hydrophilic colloid alone or from thepigmented unmodified common homogeneous solution possesses a relativelypoor color value.

Increased color value is obtained with the present printing compositionnot only when the decorated fabric is dried at elevated temperatures butalso when it is dried at room temperatures, at which the improvement ismore apparent. Our printing paste, with its discontinuous structure,produces prints that are equally brilliant and full whether the printedfabric is dried in the air or in a heated oven. This characteristic isespecially important in those processes, e. g., screen or stencilprinting, in which it is customary to air-dry the colored fabric. Apigmented homogeneous solution of a hydrophilic colloid alone or thepigmented unmodified com-- mon homogeneous solution of the twohydrophilic colloids, on the other hand, gives prints that are fairlysatisfactory when they are dried in an oven Or on steam cans but flatand lacking in brightness when they are dried at room temperatures.

Substantially any two hydrophilic colloids that form homogeneouscolloidal solutions in an aqueous medium can be employed in the presentcomposition. The combination of hydrophilic colloids must be soselected, however, that both are initially compatibly soluble in acommon aqueous medium and that one of them can be coagulated or gelledfrom such common solution under conditions under which the other of themremains in solution. In addition, of course, the hydrophilic colloidsshould be compatible with the remainder of the ingredients of the finaldispersion.

The manner in which gelation of one of the hydrophilic colloids iseffected depends largely on the nature of the two hydrophilic colloidsselected and the character of the initial common solution thereof.Either chemical or physical means may be employed to efiect suchgelation. Typical methods of introducing a discontinuous structure intothe initial common homogeneous colloidal solution comprise adjustment ofthe alkalinity or acidity of the initial solution, ad dition of awater-soluble salt thereto, addition of a water-miscible organic liquidto the initial solution, and the like. The following combinations of twohydrophilic colloids are representative of those falling within thescope of our invention:

I. An alkaline solution of an alkali-soluble. water-insoluble alkydcellulose ether such as alkali-soluble, water-insoluble hydroxyethylcellulose, alkali-soluble, water-insoluble methyl or ethyl cellulose, oralkali-soluble, water-insoluble sodium carboxymethyl cellulose, isintimately mixed with a water solution of an alkali-soluble,water-soluble hydrophilic colloid such as alkaliand water-soluble methylor ethyl cellulose, alkaliand water-soluble hydroxyethyl cellulose,alkaliand water-soluble sodium carboxymethyl cellulose, sodium alginate,or a vegetable gum in proportions to provide a common homogeneouscolloidal solution thereof. This common solution is substantiallyneutralized by the addition of acid with agitation whereupon thealkali-soluble, water-insoluble material is caused to gel with theformation of a smooth paste having a heterogeneous structure when it isviewed with an ordinary compound microscope (magnification about 50times).

11. A water solution of a water-soluble carboxyalkyl cellulose ethersuch as water-soluble sodium carboxymethyl cellulose is intimately mixedwith a water solution of a water-soluble hydrophilic colloid such aswater-soluble methyl cellulose, water-soluble hydroxyethyl cellulose ora vegetable gum that is not coagulated or gelled by a salt containing apolyvalent metal, in proportions to provide a common homogeneouscolloidal solution thereof. Upon the addition 01' a salt containing apolyvalent metal such as aluminum acetate or sodium aluminate to thiscommon solution, the water-soluble carboxyalkyl cellulose ether isthrown out of solution with the formation of a smooth mixture having aheterogeneous structure.

III. A water solution of sodium alginate is intimately mixed with awater solution of a watersoluble hydrophilic colloid such aswater-soluble droxyethyl cellulose, in water in which an alkal methylcellulose, water-soluble hydroxyethyl cellulose or a vegetable gum thatis not coagulated or gelled by polyvalent cations in proportions toprovide a common homogeneous solution thereof.

Upon the addition of a salt of a polyvalent metal such as calciumchloride, the sodium alginate is thrown out of solution with theformation of a smooth mixture having a heterogeneous structure. l

IV.- A water solution of a water-soluble hydrophilic colloid such aswater-soluble hydroxyethyl cellulose or water-soluble sodiumcarboxymethyl cellulose that can be gelled by the addition of awater-miscible alcohol aldehyde or ketone is intimately mixed with awater solution of a watersoluble hydrophilic colloid such aswater-soluble methyl or ethyl cellulose that is not gelled by theaddition of a water-miscible alcohol, aldehyde or ketone in proportionsto provide a common homogeneous colloidal solution thereof. U on theaddition of a water-miscible alcohol. aldehyde or ketone, the formermaterial is thrown out of solution in such a manner as to produceasmooth mixture with a heterogeneous structure. Each of thesecombinations of two hydrophilic colloids, when modified as indicated andthe resulting heterogeneous mixture suitably pigmented, produces a printof improved color value over that obtained when either hydrophiliccolloid is used alone or when the common homogeneo s solution of bothhydrophilic colloids is used. We have obtained unusually good results,however, with the use, of a pigmented homogeneous colloidal solution ofan alkali soluble, water-sol ble alkyl cellulose, particularly alkaliandwatersoluble methyl cellulose, in water in which an alkali-soluble,water-insoluble hydroxyalkyl cellulose, particularly alkali-soluble.water-insoluble hydroxyethyl cellulose, has been gelled byneutralization of the initial common homogeneous colloidal alkalinesolution of both cellulose ethers. Advantageously, we employ alow-viscosity type of methyl cellulose and a hydroxyethyl cellulose thatis prepared so as to be soluble in a relativelv low concentration ofalkali. We have also obtained especially good results with the use of apigmented homogeneous colloidal solution of an alkali-soluble,water-soluble hydroxyalkyl cellulose, particularly alkaliandwater-soluble hysoluble, water-insoluble hydroxyalkyl cellulose,

particularly alkali-soluble, water-insoluble hydroxyethyl cellulose, hasbeen gelled by neutralization of the initial common homogeneouscolloidal alkaline solution of both cellulose ethers. In addition to avery marked improvement in color value, prints prepared from suchpigmented dispersions, in which a water-soluble thermosetting resin hasalso been incorporated, possess an unusual degree of resistance tocrocking and washing.

Another important feature of the present invention is that therheological properties, notably the viscosity and the yield value, ofthe resulting printing paste can be readily controlled so as to impartimproved printing qualities thereto. The efiects of this control of therheological properties of our textile-decorating composition can beobserved in the increased color value and the sounder coverage obtainedand in the almost complete elimination of flocculation and migration ofthe pigment upon application of the composition to a fabric and upondrying of the decorated fabric.

The following example is illustrative of this control of rheologicalproperties possible with our invention: In the use of a low-viscositytype of a water-soluble cellulose ether such as methyl cellulose, a.concentration of 12 to 15% is necessary to provide a printing pastehaving a satisfactory printing viscosity. If the concentration of thecellulose ether is reduced by the use of a highviscosity type in orderto lower the cost of the composition, for example, then, although theprinting paste may have the proper printing viscosity, the resultingprint has little color value for practical urposes. If, however, acomriion homogeneous' colloidal solution is prepared by mixing a watersolution of such a low-viscosity type of an alkaliand water-solublecellulose ether with an alkaline solution of an alkali-soluble,water-insoluble cellulose ether, such as hydroxyethyl cellulose, and thealkali-soluble, water-insoluble cellulose ether is gelled byneutralization of the common alkaline solution, then a printing pastehaving the necessary printing viscosity can be prepared with a totalconcentration of cellulosic material ranging from 1 to 6%. The resultingcomposition gives prints of excellent color value and, when it iscompounded with a water-soluble thermosetting resin, produces printshaving unusually good fastness to crocking and washing.

If the alkali-soluble, water-insoluble cellulose ether is gelled fromits alkaline solution alone, a lumpy stringy gel of little use in thepreparation of textile-decorating compositions is formed. When, however,the alkali-soluble, water-insoluble cellulose ether is gelled from acommon alkaline solution with an alkaliand water-soluble celluloseether, the entire solution is evenly thickened, and a smooth paste ofexceptional usefulness is obtained. Moreover, the resulting paste isshorter and less tacky and thus possesses improved printing qualities.

The description of our invention has been'based so far principally onits application in the printing of textiles and other fabrics since ourcomposition possesses so many advantages in this field. The use of ourinvention is equally applicable in the dyeing of fabrics, and a definitecontrol and substantial elimination of the migration of the pigmentduring drying of the pigment-dyed fabric are accomplished with thepresent procedure. By no means is our invention to be limited to eitherfield although it is possible that, under a given set of conditions, itmay have a greater application in one field than in the other.

In the preparation of the present composition, separate aqueoussolutions of the two selected hydrophilic colloids one of which must bewatersoluble, of the water-soluble thermosetting resin, and of thewater-soluble salt, if such a coagulating 'or gelling medium is to beused, are advantageously preliminarily prepared. The pigment can beprepared in paste form by mixing a precipitate of the pigment, e. g., apress cake thereof, and a suitable dispersing agent with sufilcientwater to form a paste of the desired consistency and then grinding themixture until the pigment is in a finely divided condition; or thepigment can be otherwise prepared in a readily dispersible form. Thesolutions of the two hydrophilic colloids are mixed to form a. commonhomogeneous colloidal solution thereof; and one of the two hydrophiliccolloids is then gelled, to provide the desired discontinuous structure,in any appropriate manner as by neutralization or by addition of a saltsolution or of a water-miscible organic liquid as the case may be.Agitation of the initial common solution during gelation of one of thehydrophilic colloids is helpful in providing a smooth paste of uniformconsistency. The resin solution and the pigment dispersion are thenadded in turn to the resulting paste, to which water can be added toprovide a decorating composition having the desired dyeing or printingconsistency. A resinification catalyst, such as a suitable acidicsubstance, may be incorporated, advantageously in the form of an aqueoussolution, in the composition if desired. The several ingredients may,however, be otherwise admixed, care being taken that the pigment isproperly dispersed in the final composition.

Where the present composition is to be utilized in the printing of afabric, it can be applied in any convenient manner as from an intagliocylinder, with the use of a screen or a stencil, or the like. Where thecomposition is employed in the dyeing of a fabric, it can be applied bymeans of a pad-dyeing operation; or it can be deposited on the fabric inthe form of a thin film by transfer from a roll-coating machine. Thedecorated fabric can be dried at either elevated or normal atmospherictemperatures, whichever may be applicable to a given decoratingprocedure. Regardless of whether a fabric decorated with the presentcomposition is passed through a drying oven or over a drying can or isallowed to dry in the air, a clear, full, even color is obtained; and noflocculation or migration of the pigment is evident.

The concentration of each hydrophilic colloid contained in our pigmentedcomposition should, of course, be sufiicient to permit the formation ofthe desired discontinuous structure in the initial common homogeneouscolloidal solution thereof and to provide the necessary viscosity in theresulting paste. Where the hydrophilic colloid is obtainable in severalforms of varying viscosity. as is the case with the cellulose others,then the viscosity type of the particular cellulose ether should also betaken into consideration, for the concentration of cellulose ether isdependent thereon.

In the case of the alkyl celluloses, each of which is obtainable in awide range of viscosities, this viscosity factor is important in anotherrespect, namely, the color value of the resulting decorated fabric. Thehigher viscosity types of alkyl celluloses, such as methyl cellulose,appear to produce a finished fabric having a somewhat less color valuethan do the lower viscosity types. For example, we have found that, withmethyl cellulose, the low viscosity types (15 and 25 centipoises) andthe medium viscosity types (100 and 400 centlpoises) can be moreadvantageously employed than the high viscosity types'(1500 and 4000centipoises) (These viscosity types represent those presentlycommercially available and sold under the trade name Methocel." Theviscosity of each type is the average viscosity of a 2% aqueous solutionthereof at 20 0.). With respect to the hydroxyalkyl and the carboxyalkylcelluloses, however, this viscosity factor does not appear to have thiseffect; for substantially equivalent results are obtained whether alow-viscosity or a high-viscosity type is used.

The concentration range of the water-soluble thermosetting resin dependsnot only on the particular resin employed and on the type of fabricbeing decorated but also on a number of other factors. In general, thelower limit of concentration depends on the desired or requiredwashfastness of the finished fabric. The upper limit of concentrationdepends primarily on the maximum stiffness permissible in the finishedfabric. Generally, the preferred range of resin concentrate is .on theorder of 1 to 10% by weight, the particular concentration employeddepending largely on the nature of the particular application.

Various types of fabrics can be decorated by means of the presentprocess and the application of our invention is not limited to anyparticular fabric. Excellent color value without migration andflocculation of the pigment are obtained equally well whether the fabricbeing decorated is composed of natural fibers such as cotton, flax,wool, and hair fibers, of synthetic fibers such as regeneratedcellulose, cellulose acetate, polyamide, protein polymer, vinyl polymer,and the like fibers, of inorganic fibers such as glass, mineral, ormetal fibers, or of mixtures of such fibers. Furthermore, theapplication of our process is not limited to the usual types of woven orknitted fabrics but may also be used to decorate pile fabrics, paper, orfabrics made by processes such as combing, matting, or felting, e. g., afabric composed of loosely meshed cotton fibers bonded together by thelocalized application of a resin. The present process, moreover, isequally applicable whether a light or a heavy fabric is being decorated.(The term fabric" as used in the claims includes all these various typesof materials as well as yarns, to the decorating of which our process isalso applicable.)

The following examples are typical illustrations of the application ofour invention (parts by weight in all examples) EXAMPLE I A. Clearcontaining 5 cellulosic derivatives and 1 thermosetting resin Thisclear, when properly pigmented, produces pigment prints which showexcellent color value and, when properly cured, possess outstandingfastness to cracking and washing. An important characteristic of thispigmented clear is its ability to give prints of undiminished colorvalue upon air-drying, a feature that is especially important in thepreparation of screen prints, an operation in which it is customary toair-dry the prints before curing.

This clear is preparing by first mixing the following:

10% solution of alkali-soluble, water insoluble hydroxyethyl cellulosein 4% 3. Print colors containing up to 3 or 4% pigment These colors areprepared by mixing Clear A with the proper amounts of water-extendibledispersions of each of the following pigments: carbon black, copperphthalocyanine green, and a vat yellow (Color Index'Prototype Number105). 3 parts of a 5% aqueous solution of diammonium phosphate are addedto 100 parts of each of the print colors.

C. Three-color screen prints on mercerized cotton table-cloth The threecolors described in B are each applied to mercerized cotton table-clothfabric by the use of screen stencils of the type customarily used formaking screen prints. The printed fabric is allowed to dry in the air,and the resin is finally cured by heating the driell fabric in a curingoven at 300 F. for 2 minutes. The resulting printed fabric hasexceptionally good color value and possesses excellent resistance towashing and crocking.

EXAMPLE2 A clear is prepared as in Example 1A, except that thethermosetting resin is omitted, and three print colors are compoundedfrom this clear as in Example 13. These three colors are applied to acotton fabric by the use of screen stencils, and the printed fabric isair-dried as in Example 10. Good color value is obtained in theresulting finished fabric, which, although resistant to dry-crocking, isnot particularly fast to wet-crocking or to washing.

EXAMPLE 3 A. Clear containing 10% cellulosic derivatives and 2%thermosetting resin for use in printing deep shades The followingingredients are first thoroughly mixed:

10% solution of alkali-soluble, waterinsoluble hydroxyethyl cellulose in4% B. Print colors containing up to 5% pigment These colors are preparedby mixing Clear A with the proper amounts of water-extendibledispersions of each of the following pigments: metallizedalpha-nitroso-beta-naphthol iron oxide yellow, and an azo violet(prepared by coupling 5-nitroso-2-amino anisole with2,3-oxynaphthoic-alpha-naphthalide). 3 parts 01' a 5% aqueous solutionof diammonium phosphate are added to 100 parts of each of the printcolors.

C. Three-color roll prints .on drapery fabric The three colors describedin B are each applied to a drapery fabric using engraved print rolls.The printed fabric is dried on steam can! or in an oven. Finally, theresin is cured by heating the dried fabric in a curing oven for 2minutes at 350 F. The resulting printed fabric has good color value,lighti'astness and w'ashfastness and, even though the shades are deep.excellent resistance to crocking.

EXAMPLE 4 A. Clear containing 4% cellulosic derivatives and 2%thermosetting resin This clear is prepared by first mixing:

10% solution of alkali-soluble water-insoluble hydroxyethyl cellulose in4% aqueous sodium hydroxide 15.0 10% aqueous solution of alkaliandwatersoluble hydroxyethyl cellulose 25.0 Water 46.0

The resulting solution is neutralized by the addition 01.:

10% orthophosphoric acid (approx.) 6.0

To the neutral mixture are added: 7

50% aqueous solution of water-soluble polyhydric alcohol-modifiedurea-formaldehyde resin 4.0 The weight is adjusted to by mixing in:

Water (approx)..- 4.0

B. Print colors Three colors are prepared as in Example 18 except thatClear 4A is used instead of Clear 1A.

, c. Prints Prints may be made as in Example 10 and similarly possessgood color value and exhibit excellent resistance to crocking andwashing.

Moreover, prints made with the present colors show some fastness evenwhen air-dried or when dried and cured at relatively low temperaturesEXAMPLE 5 A. Clear containing 2% cellalosic derivatives and 1%thermosetting resin for use in preparing prints in medium and lightshades The following are first mixed:

10% solution of alkali-soluble, water-insoluble hydroxyethyl cellulosein 4% aqueous sodium hydroxide 10.0 3% aqueous solution of alkaliandwatersoluble hydroxyethyl cellulose 33.3 Water 44.7

The resulting solution is neutralized by the addition of:

10% orthophosphoric acid approx.)

To the neutral mixture are added:

50% aqueous solution of water-soluble polyhydric alcohol-modifiedurea-formaldehyde resin The weight is adJusted to 100 by mixing in:

Water (approx) 11 B. Print color A print color is prepared by mixingClear A with a water-extendible dispersion of a pigment, for example,iron oxide red, in such proportions as to give, for example, 0.25%pigment.

C. Single-color blotch print on cotton sheeting The color described in Bis applied to a fabric, e. g., cotton sheeting, with a blotch-printroll. The printed fabric is dried by passage over steam cans, and theresin is finally cured by heating the dried fabric 2 minutes at 350 F.An evenly colored fabric showing excellent color value and goodresistance to crocking and washing'is obtained.

EXAMPLE 6 A. Clear containing 5% cellulosic derivatives and 2%thermosetting resin for printing medium and light shades This clear isprepared by first mixing: 3% aqueous solution of water-soluble sodium E.Print colors Three colors are prepared as in Example 13 except thatClear 6A is used instead of Clear 1A.

C. Prints A print is made as described in Example 10. The finishedfabric has a full. even color and excellent crockand washfastness.

EXAMPLE 7 A. Clear prepared from methyl cellulose, sodium alginate, andurea-formaldehyde resin, suitable for printing medium and light shadesThe following three ingredients are first mixed:

3% aqueous solution of sodium alginate 10.0 10% aqueous solution of 25cps. water-soluble methyl cellulose 40.0

Water 42.0

To the resulting solution are added:

5% aqueous solution of calcium chloride 6.0

To the resulting paste are added:

50% aqueous solution of water-soluble polyhydric alcohol-modifiedurea-formaldehyde resin 2.0

12 3. Print colors Colors are prepared as in Example 18 except thatClear 7A is used instead of Clear 1A.

c. Prints Aprint is made as described in Example 10, and the finishedfabric again possesses good color and a high degree of resistance tocrocking and washing.

EXAMPLE 8 A. Clear for printing medium and light shades The followingare mixed in the order indicated:

3% aqueous solution of water-soluble sodium carboxymethyl cellulose 60.010% aqueous solution of 25 cps. water-soluble methyl cellulose 12.0Isopropyl alcohol 24.0 50% aqueous solution of water-soluble polyhydrlcalcohol-modified melamine formaldehyde resin 4.0

13. Print colors Print colors containing up to about 3% pigment areprepared by mixing Clear A with waterextendible dispersions of each ofthe following pigments: copper phthalocyanine green iron oxide red, andcarbon black. About 3 parts of 5% diammonium phosphate to 100 parts ofeach print color are added.

C. Three-color print on spun-rayon scarf fabric The three colorsdescribed in B are printed with silk screen stencils on a. spun-rayonscarf fabric. The printed fabric is allowed to air-dry, and the resin iscured by heating the dried fabric to 300 F. for 3 minutes. The resultingprinted fabric has excellent color value and'shows good fastness to theusual cleaning procedures and to crocking.

EXAMPLE 9 A. Clear containing 5% cellulosic derivatives and 12.5%thermosetting resin for pad-dyeing medium to heavy shades The followingare mixed:

10% solution of alkali-soluble. water-insoluble hydroxyethyl cellulosein4% aqueous sodium hydroxide 20.0

10% aqueous solution of 15 cps. alkaliand water-soluble methyl cellulose30.0

Water 15.0

The resulting solution is neutralized by the addition of:

10% orthophosphoric acid (approx.) 8.0

To the neutral mixture are added:

50% aqueous solution of water-soluble polyhydric alcohol-modifiedmelamine-formaldehyde resin.. 25.0

. The weight is adjusted to 100 by mixing in:

Water ...L (approx.) 2.0

B. Padding liquor A padding liquor containing 0.5% by weight of a vatblue is prepared with the following ingredients, which are mixed in theorder indicated:

C. Pad-dyeing This padding liquor is applied to a fabric, for example,spun-rayon dress goods, by means of a three-roll padder. The wet dyedfabric is dried by passage over steam cans. Finally, the resin is curedby subjecting the dried fabric to a temperature of 350 F. for 2 minutesin a curing oven.

The finished fabric shows full color value, and there is no evidence ofmigration or flocculation of the pigment.

This application is a divisional application of application Serial No.680,056, filed June 28, 1946, now Patent 2,527,530.

We claim:

1. A fabric-decorating composition comprising a water-insoluble pigmentdispersed in a vehicle comprising a heterogeneously gelatinizedwatersoluble sodium alginate dispersed in an aqueous colloidal solutionof a non-gelatinized watersoluble cellulose ether, said colloidalsolution having dissolved therein a polyvalent metal salt as agelatinizing agent for the gelatinized sodium alginate.

2. A fabric-decorating composition as claimed in claim 1, wherein thenon-gelatinized watersoluble cellulose ether is water-solublehydroxyethyl cellulose.

3. A fabric-decorating composition as claimed in claim 1, wherein awater-soluble thermosetting resin is dissolved in the aqueous solution.

4. A vehicle for use in a fabric decorating composition comprising aheterogeneously gelatinized sodium alginate dispersed in an aqueouscolloidal solution of a non-gelatinized water-soluble cellulose ether,said colloidal solution having dissolved therein a polyvalent metal saltas a gelatinizing agent for the gelatinized sodium alginate;

5. A vehicle as claimed in claim 4. wherein the non-gelatinizedwater-soluble cellulose ether is water-soluble hydroxyethyl cellulose.

6. A vehicle as claimed in claim 4, wherein a water-solublethermosetting resin is dissolved in the aqueous solution.

7. The method of decorating a fabric to obtain a full even color valuethereon, which comprises applying to the fabric a water-insolublepigment dispersed in a vehicle comprising a heterogene- 14 ouslygelatinized sodium alginate dispersed in an aqueous colloidal solutionof a non-gelati nized water-soluble cellulose ether, said colloidalsolution having dissolved therein a polyvalent metal salt as agelatinizing agent for the gelatinized sodium alginate.

8. The method as claimed in claim 7. wherein the non-gelatinizedwater-soluble cellulose ether is water-soluble hydroxyethyl cellulose.

9. The method as claimed in claim 7, wherein a water-solublethermosetting resin is dissolved in the aqueous solution.

10. The method of preparing a fabric-decorating composition comprisingforming a common homogeneous aqueous colloidal solution of sodiumalginate and of a water-soluble cellulose ether, adding a polyvalentmetal salt as a gelatinizing agent will heterogeneously gelatinize thesodium alginate to yield a dispersion of heterogeneously gelatinizedsodium alginate dispersed in an aqua" ous colloidal solution ofnon-gelatinized watersoluble cellulose ether, and then dispersing awater-insoluble pigment in the dispersion.

11. The method as claimed in claim 10, in which the non-gelatinizedwater-soluble cellulose ether is water-soluble hydroxyethyl cellulose.

12. The method as claimed in claim 10, in which a water-solublethermosetting resin is dissolved in the aqueous solution.

13. The method of controlling the rheological properties of aheterogeneous gelatinous dispersion of sodium alginate in an aqueouscolloidal solution of a non-gelatinized water-soluble cellulose ether,which comprises forming a common homogeneous aqueous colloidal solutionof sodium alginate and of a water-soluble cellulose ether, adding a,polyvalent metal salt as a gelatinizing agent which will heterogeneouslygelatinize the sodium alginate to yield a dispersion of heterogeneouslygelatinized sodium alginate dispersed in an aqueous colloidal solutionof non-gelatinized water-soluble cellulose ether, and then dispersing awater-insoluble pigment in the dispersion.

14. The method as claimed in claim 13, in

which the non-gelatinized water-soluble cellulose ether is water-solublehydroxyethyl cellulose.

15. The method as claimed in claim 13, which includes the step ofdissolving a water-soluble thermosetting resin in the aqueous solution.

NORMAN S. CASSEL. ALFRED T. CLIFFORD.

Name Date Number Reichel June 10. 1941

1. A FABRIC-DECORATING COMPOSITION COMPRISING A WATER-INSOLUBLE PIGMENTDISPERSED IN A VEHICLE COMPRISING A HETEROGENEOUSLY GELATINIZEDWATERSOLUBLE SODIUM ALGINATE DISPERSED IN AN AQUEOUS COLLOIDAL SOLUTIONOF A NON-GELATINIZED WATERSOLUBLE CELLULOSE ETHER, SAID COLLOIDALSOLUTION HAVING DISSOLVED THEREIN A POLYVALENT METAL SALT AS AGELATINIZING AGENT FOR THE GELATINIZED SODIUM ALGINATE.
 3. AFABRIC-DECORATING COMPOSITION AS CLAIMED IN CLAIM 1, DISSOLVED IN THEAQUEOUS SOLUTION.